Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
  • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
  • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
  • C10M129/86—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
  • C10M129/92—Carboxylic acids
  • C10M129/93—Carboxylic acids having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
  • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
  • C10M145/16—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate polycarboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
  • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/22—Acids obtained from polymerised unsaturated acids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
  • C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid

Definitions

• the present invention relates generally to compositions produced from ⁇ , ⁇ -unsaturated dicarboxylic compounds and olefinically unsaturated compounds, which compositions possess properties making them particularly suitable for use as lubricants and lubricant additives.
• compositions comprising reaction products of ⁇ , ⁇ -unsaturated dicarboxylic compounds and olefinically unsaturated compounds are generally known in the art. These reaction products have been described in the literature as having a large number of uses ranging from lubricants to emulsifiers, coating additives to cosmetics, protective colloids to dispersants, and detergents to plasticizers.
• reaction products i.e. intermediates in the production of polycondensation products
• GB 1 173 643 discloses a specific, high pressure process which produces unsaturated tetracarboxylic acids by reacting an olefin with a 1,2-unsaturated 1,2-dicarboxylic acid or a functional derivative thereof.
• Suitable reactants to produce the tetracarboxylic acids are lower alkyl olefins.
• Preferred are branched olefins, with the olefin exemplified being isobutene.
• compositions produced by these known reaction schemes comprise essentially one or both of only two types of reaction products--lower molecular weight ene (alkenyl succinic) products and higher molecular weight polymerization products.
• the difference between producing the lower molecular weight alkenyl succinic product and the higher molecular weight polymerization products is normally due to the presence or absence of a polymerization initiator in the reaction mixture.
• esters are recognized to be less reactive with olefins than their acid and anhydride counterparts.
• This prejudice to the use of esters in an ene selective reaction scheme is also apparent from previously mentioned GB 1 173 643.
• GB 954 901 makes a distinction between various carboxylic compounds and, in line with further prior art, does not actually make use of esters, teaching that carboxylic anhydrides are to be preferred.
• esters are further utilized only in the polymerization reactions as described, for example, in previously incorporated DE-A-3223694.
• compositions can be prepared as is further described below which comprise a substantial amount of an intermediate molecular weight reaction product which is neither the known lower molecular weight alkenyl succinic nor the known higher molecular weight polymeric reaction product.
• composition suitable for use as a lubricant or lubricant additive which composition comprises the reaction product of (1) an ⁇ , ⁇ -unsaturated dicarboxylic compound and (2) an olefinically unsaturated compound, wherein
• the ⁇ , ⁇ -unsaturated dicarboxylic compound is comprised of at least one ester selected from the group consisting of fumaric esters and maleic esters, wherein the esterifying component comprises a monoalcohol having from 4 to 20 carbon atoms;
• the olefinically unsaturated compound comprises a monoolefinically unsaturated compound having from 12 to 24 carbon atoms;
• the composition comprises a substantial amount of an intermediate molecular weight reaction product of (1) and (2) which intermediate molecular weight reaction product is neither the lower molecular weight ene reaction product nor the higher molecular weight polymerization product of (1) and (2).
• compositions in accordance with the present invention In order to prepare the compositions in accordance with the present invention generally three routes can be followed, viz. (i) reacting (1) and (2) in the presence of a polymerization inhibitor, (ii) reacting (1) and (2) under the exclusion of oxygen, or (iii) stepwise dosage of the ester (1) to the reaction mixture comprising olefin (2).
• said routes may be combined in any possible manner, e.g. stepwise dosage of the ester (1) to the reaction mixture comprising olefin (2) and a polymerization inhibitor.
• compositions in accordance with the present invention are preferably produced by reacting (1) and (2) in the presence of an effective amount of a polymerization inhibitor.
• compositions in accordance with the present invention find utility in a wide variety of fields ranging, for example, from lubricants to emulsifiers, coating additives to cosmetics and detergents to plasticizers. As indicated before, however, they have been found especially suitable for use as lubricants and lubricant additives, particularly in low viscosity lubricant applications such as in engine oils, gear oils, greases, compressor oils, turbine oils, metal working fluids, machine oils and hydraulic fluids.
• the alkenyl and alkyl succinic compounds are characterized by high volatility, high color, high acid values, very low viscosity and less than optimal lubrication performance.
• compositions in accordance with the present invention overcome these disadvantages by providing a balance of desirable properties such as, for example, viscosity, viscosity index, pour point, volatility and lubricity, which would not be expected based upon the properties of the known lower molecular weight alkenyl and alkyl succinic products and higher molecular weight polymerization products.
• composition suitable for use as a lubricant or lubricant additive which composition comprises the reaction product of (1) an ⁇ , ⁇ -unsaturated dicarboxylic compound and (2) an olefinically unsaturated compound, wherein
• the ⁇ , ⁇ -unsaturated dicarboxylic compound is comprised of at least one ester selected from the group consisting of fumaric esters and maleic esters, wherein the esterifying component comprises a monoalcohol having from 4 to 20 carbon atoms;
• the olefinically unsaturated compound comprises a mono olefinically unsaturated compound having from 12 to 24 carbon atoms;
• the composition comprises a substantial amount of an intermediate molecular weight reaction product of (1) and (2), which intermediate molecular weight reaction product is neither the lower molecular weight ene reaction product nor the higher molecular weight polymerization product of (1) and (2).
• suitable ⁇ , ⁇ -unsaturated dicarboxylic compounds are fumaric and maleic esters, which include both the monoesters and diesters of fumaric acid, maleic acid and maleic anhydride.
• the diesters are preferred due to their better stability under more severe conditions. Especially preferred are the fumaric diesters.
• suitable monoalcohols having from 4 to 20 carbon atoms may be mentioned linear, branched and/or cyclic monoalcohols such as butanols, ethylhexanols, neopentyl alcohols, isodecyl alcohols, phenols and cyclohexanols. More preferred of these are the monoalcohols having from 4 to 12 carbon atoms, and especially from 4 to 8 carbon atoms. Most preferred are 1-butanol and 2-ethylhexanol. Further, it is advantageous to make use of alcohols alkoxylated with from 1 to 10 ethoxy or propoxy units. The original alcohol moiety may then have from 1 to 20 carbon atoms.
• the fumaric and maleic esters, component (1) above, may be produced by the esterification of the appropriate of fumaric acid, maleic acid or maleic anhydride. Such esterification reaction is well known to those skilled in the art and need not be further detailed herein.
• component (2) above may be mentioned a wide variety of ⁇ -olefins, internal olefins and vinylidene compounds, as well as other branched, aromatic and heterosubstituted monoolefins and mixtures thereof, a number of which are specifically disclosed in many of the previously incorporated U.S. Pat. No. 3,412,111, U.S. Pat. No. 4,192,930, U.S. Pat. No. 4,396,774 and U.S. Pat. No. 4,761,488.
• Particularly preferred are ⁇ -olefins, internal olefins and vinylidene compounds having from 12 to 16 carbon atoms, an advantage to these olefins being that products are obtained which exhibit a lower pour point.
• olefins which may be obtained from various sources, e.g. Ethyl Corporation, Shell Chemical Co., UOP and Chevron Chemical Co., to name a few
• olefins are generally mixtures characterized by a predominant olefin species and a predominant or average carbon number content.
• Such commercially available mixtures comprising in substantial part ⁇ -olefins with minor amounts of internal olefins and vinylidene compounds are particularly preferred. Further information regarding mixed olefins may be obtained from Kirk-Othmer Encyclopedia of Chemical Technology, (1981), Vol. 16, pages 480-499.
• ⁇ -olefins may be mentioned 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene. Preferred among these are the C12 to C16 ⁇ -olefins, with the C14 to C16 ⁇ -olefins being most preferred.
• components (1) and (2) are reacted in the presence of an effective amount of a suitable polymerization inhibitor.
• a suitable polymerization inhibitor such as the hydroxy aromatic and amino aromatic compounds as disclosed in previously incorporated U.S. Pat. No. 3,412,111.
• hydroquinone, p-tert.butylcatechol and p-hydroxyanisole are preferred, with hydroquinone being most preferred.
• an effective amount is it meant an amount of polymerization inhibitor sufficient to result in the production of a substantial amount of the intermediate molecular weight reaction product.
• the amount of inhibitor utilized may vary widely, but is preferably in the range of from about 0.01% to about 3% by weight, more preferably from about 0.05% to about 2% by weight, and most preferably from about 0.1% to 1% by weight, based upon the combined weight of components (1) and (2).
• reaction of components (1) and (2) should take place in the substantial absence of the polymerization initiators.
• Polymerization initiators are well-known in the art and need not be detailed further.
• the reaction between components (1) and (2), in the presence of the polymerization inhibitor is preferably conducted at temperatures from about 180° C. to about 350° C. and, more preferably, from about 200° C. to about 270° C.
• the reaction may be carried out at subatmospheric, atmospheric or superatmospheric pressures, but preferably atmospheric.
• the reaction preferably is carried out in the absence of oxygen, i.e. under an inert (nitrogen) atmosphere. Reaction times may vary widely, generally ranging from about 0.5 to about 15 hours and, more preferably, from about 5 to about 12 hours, with the longer reaction times required for the lower reaction temperatures.
• Components (1) and (2) may be reacted in widely varying molar ratios, but generally ranging from about 0.15/1 to about 6.0/1, preferably from about 0.25/1 to about 4.0/1, and more preferably from about 0.5/1 to about 2.0/1. Components (1) and (2) may be reacted in a single dose or may be dosed continuously or periodically throughout the reaction cycle. Stepwise dosage of component (1) to the reaction mixture containing (2) is preferred.
• compositions resulting from the reaction of components (1) and (2) when produced in accordance with the present invention, comprise a substantial amount of an intermediate molecular weight reaction product, which is distinguishable from the known lower molecular weight ene reaction product and higher molecular weight polymerization reaction products of the same components.
• the compositions produced in accordance with the present invention may also contain amounts of one or more of these known lower and higher molecular weight products.
• compositions in accordance with the present invention preferably comprise at least about 30% by weight, more preferably at least about 40% by weight, and still more preferably at least about 50% by weight, of the intermediate molecular weight reaction product, and up to about 70% by weight, more preferably up to about 60% by weight, and still more preferably up to about 50% by weight, of the lower molecular weight reaction product.
• % by weight is based upon the total weight of the reaction products.
• the intermediate molecular weight reaction product primarily comprises compositions of 3-5 monomeric units, the intermediate molecular weight reaction product overall having a number average molecular weight (Mn) in the range of about 600 to about 1500. Further, it has been found that, of these compositions having 3-5 monomeric units, a greater proportion of the monomeric units are ester-based monomeric units.
• the intermediate molecular weight reaction product includes compositions such as:
• compositions in accordance with the present invention may additionally be hydrogenated, for example by heating at 130°-200° C. in the presence of a catalyst, e.g., nickel or palladium.
• a catalyst e.g., nickel or palladium.
• compositions in accordance with the present invention possess properties making them distinguishable from those compositions produced in accordance with the known "ene” selective reactions or the known polymerization selective reactions.
• compositions were produced from different ⁇ , ⁇ -unsaturated dicarboxylic compounds and olefinically unsaturated compounds as set forth below and in Tables I-XII.
• compositions (1) were tested for:
• pour point hydrogenated (°C.)--the products were subsequently hydrogenated with PD/C as catalyst, at 150° C., under normal pressure and for about 3 hours.
• the hydrogenated products were tested for pour point as above.
• the mixture was then heated to 230° C. for 10 hours, after which the remaining volatiles were removed up to 240° C. in vacuo.
• the product yield for the process in accordance with the present invention was, in each case, between about 70%-75%. Product yield in these examples is based upon the total weight of the raw materials.
• Step 1- reaction of maleic anhydride and olefin in the presence of polymerization inhibitor
• the product yield after Step 1 was, in each case, between about 70%-75%.
• reaction was carried out as described above for the process in accordance with the present invention, except that no polymerization inhibitor or xylene was added to the reaction mixture.
• the product yield was, in each case, between about 70%-75%.
• the product yield was, in each case, between about 85%-90%.
• Table X shows that products according to the invention are prepared provided the inhibitor is present, oxygen is excluded or the ester is dosed.
• the product at the bottom of Table X is not in accordance with the present invention.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Lubricants (AREA)

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• 1990
  • 1990-11-09 US US07/611,240 patent/US5176841A/en not_active Expired - Lifetime
  • 1990-11-12 AT AT90202980T patent/ATE132130T1/de not_active IP Right Cessation
  • 1990-11-12 DE DE69024465T patent/DE69024465T2/de not_active Expired - Fee Related
  • 1990-11-12 ES ES90202980T patent/ES2081343T3/es not_active Expired - Lifetime
  • 1990-11-12 EP EP90202980A patent/EP0429123B1/de not_active Expired - Lifetime
  • 1990-11-16 CA CA002030130A patent/CA2030130C/en not_active Expired - Fee Related
  • 1990-11-16 JP JP2308949A patent/JP2916244B2/ja not_active Expired - Fee Related

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